CN109851760A - Cation-modified epoxy resin, modified epoxy polymer, lotion and preparation method thereof and coating and application - Google Patents
Cation-modified epoxy resin, modified epoxy polymer, lotion and preparation method thereof and coating and application Download PDFInfo
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Abstract
The present invention provides a kind of cation-modified epoxy resin, modified epoxy polymer, lotion and preparation method thereof and coating and applications.Cation-modified epoxy resin: epoxy resin compound, basic catalyst, aminated compounds and end amino-type acrylonitrile-butadiene copolymer.Modified epoxy polymer: cation-modified epoxy resin, isocyanate curing agent, epoxy resin compound, basic catalyst, acid, aminated compounds.Lotion: pure water, acid, cation-modified polybutadiene epoxy resin, modified epoxy polymer and deionized water.The application of coating is used for cathode electro-coating.Cation-modified epoxy resin provided by the present application, modified epoxy polymer, lotion and preparation method thereof and coating, water-tolerant, VOC content are low, levelling appearance is good, high throwing power, high sharp edge anti-corrosive properties, the excellent characteristics such as good to good combination power, the shock resistance of substrate.
Description
Technical field
The present invention relates to paint fields, poly- in particular to a kind of cation-modified epoxy resin, modified epoxy
Close object, lotion and preparation method thereof and coating and application.
Background technique
Electrophoretic coating is since being widely used in using car body and automobile component as the field of main application, so far
The electrophoretic coating with various properties is had developed.In a manner of electrophoretic painting especially based on cathode electrophoresis dope, from
The sixties in last century put into industrial production since since its film performance is excellent, utilization efficiency of coatings is high and low VOC content etc. is excellent
Point develops very fast.Now cathode electrophoresis dope to be widely used in body of a motor car, vapour rub accessory, household electrical appliances, furniture part,
Industries and the fields such as hardware electromechanics, military project.
That there is VOC emission amounts is big for existing coating, the steady film property of coating is poor, coatings thickness fluctuation is larger, film is soft
Toughness is poor and the problems such as to the wetting and poor binding ability of substrate.Known conventional cathode electrophoretic coating improves film film
Flexible and levelability method is usual are as follows: epoxy resin partial open loop introduces the fatty acid or plant oil of alkyl phenol or long-chain
Or the polyetheramine of long-chain；Epoxy resin and polyalcohol bifunctional or fatty amine bifunctional carry out chain extension；Or in cathode
Plasticizer is added in electrophoretic coating, such as ester alcohol 12 (CS-12), polypropylene glycol alkyl phenyl ether etc.；These above-mentioned methods can deposit
In following defect: the performance of sacrificing cathode electrophoresis film, especially antiseptic property.Therefore, it finds one kind and is able to solve above-mentioned ask
The ingredient of topic simultaneously develops the coating haveing excellent performance as urgent problem to be solved accordingly.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of cation-modified epoxy resin, prepares modified epoxy tree as a kind of
The basic ingredient of lipopolymer.
The second object of the present invention is to provide a kind of preparation method of cation-modified epoxy resin, operation letter
It is single, safe and environment-friendly.
The third object of the present invention is to provide a kind of modified epoxy polymer, the core component as lotion.
The fourth object of the present invention is to provide a kind of preparation method of modified epoxy polymer, and technique is steady
It is fixed, easy to operate.
The fifth object of the present invention is to provide a kind of lotion, and core component of the lotion as coating is able to solve height
VOC content, the steady film property of coating are poor, coatings thickness fluctuation is larger, flexibility is poor, poor to the wetting of substrate and binding ability
The problems such as.
The sixth object of the present invention is to provide a kind of preparation method of lotion, easy to operate.
The seventh object of the present invention is to provide a kind of coating, has good water resistance, low VOC emission amount, good
Levelling appearance, high throwing power, high anti-corrosive properties, that good to good combination power, the shock resistance of substrate, Stability of Bath Solution is good etc. is excellent
Feature.
The eighth object of the present invention is to provide the application of coating described in one kind, for cathode electro-coating, Jin Erguang
It is general apply to body of a motor car, vapour rubs industries and the fields such as accessory, household electrical appliances, furniture part, hardware electromechanics, military project.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of cation-modified epoxy resin, raw material is based on parts by weight, comprising:
800-1000 parts of epoxy resin compound, 0.3-0.6 parts of basic catalyst, 40-60 parts of aminated compounds and end amine
50-200 parts of fundamental mode acrylonitrile-butadiene copolymer.
Specifically, epoxy resin compound can be 800 parts, 850 parts, 900 parts, 950 parts, 1000 parts, basic catalyst
It can be 0.3 part, 0.4 part, 0.5 part, 0.6 part, aminated compounds can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, hold amido
Type acrylonitrile-butadiene copolymer can be 50 parts, 70 parts, 90 parts, 100 parts, 120 parts, 140 parts, 160 parts, 180 parts, 200 parts.
For holding amino-type acrylonitrile-butadiene copolymer, refers to and Polybutadiene-acrylonitrile polymer is modified by amine
The polymer arrived, such as: the ATBN of U.S. CVC thermosetting property special material Co., Ltd, Goodrich Chemical company, the U.S.
ATBN etc. or its mixture.The general structure of Polybutadiene-acrylonitrile polymer is shown below:
Wherein, x1, x2, y is the number of 0.1-1, the integral multiple that M is 1.
Preferably, the epoxy resin compound is selected from bisphenol-A, Bisphenol F, bisphenol S, phenol novolaks, cresols
Linear phenol-aldehyde resin, aliphatic type monofunctional epoxy resin, aromatic type monofunctional epoxy resin and aliphatic type difunctionality ring
One of oxygen resin is a variety of；
Preferably, the basic catalyst be selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl ammonium chloride,
One of triphenylphosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine are a variety of；
It is further preferred that the aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N- methyl second
One of hydramine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
It is further preferred that the average molecular weight of the cation-modified epoxy resin is 3000-8000.
A kind of preparation method of the cation-modified epoxy resin, comprising the following steps:
The epoxy resin compound reacts under the basic catalyst existence condition obtains polyepoxides, described
Polyepoxides reacts to obtain the cation-modified epoxy with the end amino-type acrylonitrile-butadiene copolymer, the aminated compounds
Resin.
A kind of modified epoxy polymer, raw material is based on parts by weight, comprising:
Cation-modified epoxy resin 20-40 parts, 10-20 parts of the isocyanate curing agent, the esterification of the second asphalt mixtures modified by epoxy resin
8-12 parts of object 100-140 parts of conjunction, 0.3-0.6 parts of the second basic catalyst, 5-10 parts of acid and the second aminated compounds；
Specifically, cation-modified epoxy resin can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, cured with isocyanates
Agent can be 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, and the second epoxy resin compound can be 100 parts, 105
Part, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, the second basic catalyst can be 0.3 part, 0.4 part,
0.5 part, 0.6 part, acid can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and the second aminated compounds can be 8 parts, 9 parts, 10
Part, 11 parts, 12 parts；
Preferably, the acid is selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, hydrochloric acid, sulfuric acid, nitre
Acid, sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulfosalicylic acid
One of acid anhydride, Loprazolam and isethionic acid are a variety of；
Preferably, second epoxy resin compound be selected from bisphenol-A, Bisphenol F, bisphenol S, phenol novolaks,
Cresol novolaks, aliphatic type monofunctional epoxy resin, aromatic type monofunctional epoxy resin and the double officials of aliphatic type
Can epoxy resin it is one or more；
It is further preferred that second basic catalyst is selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl
One of ammonium chloride, triphenylphosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine are a variety of；Tool
Body, the second basic catalyst can be identical as basic catalyst, can also be different；
It is further preferred that second aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N-
One of methylethanolamine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
Specifically, the second aminated compounds can be identical as aminated compounds, can also be different；
Preferably, the isocyanate curing agent passes through the polyisocyanates chemical combination containing one or more isocyanate group
Object reacts to obtain with the sealer that can be added in the isocyanate group；
It is further preferred that the sealer is selected from alcohol ethers, phenol, lactams, activity methene compound, mercaptan
Class, sour amides, amine, imidazoles, ureas, carbamates, imines, oximes, sulfites and hydroximic acid esters
One of or it is a variety of.
A kind of preparation method of the modified epoxy polymer, comprising the following steps:
Second epoxy resin compound reaction under the sour existence condition obtains the second polyepoxides；
Then second basic catalyst and second aminated compounds is added, and the reaction was continued；
The isocyanate curing agent and the cation-modified epoxy resin are added after cooling, by keeping the temperature, cooling down i.e.
It can discharge.
A kind of lotion, based on parts by weight, including 25-35 parts of the first pure water, the second 4-6 parts of acid, cation change raw material
Property 50-150 parts of polybutadiene epoxy resin, 300-450 parts of the modified epoxy polymer and deionized water 250-400
Part；
Preferably, second acid is selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, hydrochloric acid, sulphur
Acid, nitric acid, sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulphophenyl
One of formic anhydride, Loprazolam and isethionic acid are a variety of.
Specifically, the first pure water can be 25 parts, 27 parts, 29 parts, 30 parts, 32 parts, 34 parts, 35 parts in emulsion materials, the
Diacid can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, cation-modified polybutadiene epoxy resin can be 50 parts, 60 parts,
70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, the modified epoxy polymer can
To be 300 parts, 320 parts, 340 parts, 360 parts, 380 parts, 400 parts, 420 parts, 440 parts, 450 parts, deionized water can be 250
Part, 270 parts, 290 parts, 310 parts, 330 parts, 350 parts, 370 parts, 390 parts, 400 parts；
Preferably, the raw material of the cation-modified polybutadiene epoxy resin is based on parts by weight, comprising: epoxy-modified
50-70 parts of polybutadiene, 0.3-1 parts of third basic catalyst, 20-60 parts of third aminated compounds, 5-20 parts of third acid
With 10-30 parts of the second pure water；
Third basic catalyst can be identical as basic catalyst, the second basic catalyst, can also be different；Third amine
Compound can be identical as aminated compounds, the second aminated compounds, can also be different；Third acid can be with acid, the second sour phase
Together, it can also be different；For pure water, the water of identical parameters can be used, the water of different parameters also can be used；
Epoxy-modified polybutadiene refers to the tree being modified by epoxy resin to polybutadiene polymers
Rouge, for example, the Ricon657 of Cray Valleylad Inc., the JP-200 of Cao Da company, Japan, contest road company PB4700 etc. one kind
Or two or more mixtures；The general structure of polybutadiene polymers is shown below:
Wherein, n, m, x are the number of 0.1-1, the integral multiple that M is 1.
Preferably, the third basic catalyst is selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl chlorine
Change one of ammonium, triphenylphosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine or a variety of；
It is further preferred that the third aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N- first
One of ethylethanolamine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
It is further preferred that the third acid is selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, salt
Acid, sulfuric acid, nitric acid, sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulphur
One of yl benzoic acid acid anhydride, Loprazolam and isethionic acid are a variety of；
It is further preferred that the average molecular weight of the cation-modified polybutadiene epoxy resin is 1000-5000.
A kind of preparation method of the lotion, comprising the following steps:
Epoxy-modified polybutadiene is under the third basic catalyst existence condition, with the third amine chemical combination
Object reaction；Then the third acid is added and second pure water reacts to obtain the cation-modified polybutadiene asphalt mixtures modified by epoxy resin
Rouge；
Add after first pure water, second acid and the cation-modified polybutadiene epoxy resin are mixed dispersion
Enter modified epoxy polymer, the deionized water is added step by step after high speed dispersion.
A kind of coating, including mill base, water and the lotion, the weight ratio of the mill base, the water and the lotion is
1:4-7:4-7；Preferably, the coating further includes additive, the additive include water-miscible organic solvent, solidification urge it is dry
One of agent, surfactant, antioxidant, UV absorbers are a variety of.
A kind of application of the coating, is used for cathode electro-coating.
Compared with prior art, the invention has the benefit that
(1) the modified epoxy polymer that cation-modified epoxy resin is prepared as key foundation ingredient, is replaced
For the effective component of existing coating, more excellent performance of coating is obtained by preparing lotion；
(2) coating have good water resistance, low VOC emission amount, good levelling appearance, high throwing power, high anti-corrosive properties,
The excellent characteristics such as good wet and binding force, shock resistance to substrate are good, Stability of Bath Solution is good；
(3) stable preparation process, easy to operate；
(4) coating has a wide range of application.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation of cation-modified epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 600 parts of the aliphatic type simple function group epoxy resin and bis-phenol that epoxide equivalent is 180
A200 parts, it is heated to 130 DEG C after being uniformly mixed, 0.6 part of N is then added, N- dimethyl benzylamine is small in 140 DEG C of heat preservations 6
When, obtain a kind of polyepoxides that epoxide equivalent is 500.40 parts of N- methylethanolamines, 200 parts of ATBN are added, at 120 DEG C
Reaction is cooled to 60 DEG C with bottom discharge after 5 hours, it is spare to obtain the cation-modified epoxy resin that average molecular weight is 3000.
The preparation of isocyanate curing agent:
4,4 ' -30 parts of methyl diphenylene diisocyanates, 30 parts, N of methyl iso-butyl ketone (MIBK) (MIBK), N dimethyl benzylamine 0.1
Part, it is heated to 90 DEG C after being uniformly mixed, is added dropwise 20 parts of sealer phenol, so that product temperatur heat preservation is dripped at 70 DEG C
Temperature is promoted afterwards to 80 DEG C, is kept the temperature 1 hour, in subsequent detection, is no longer detected NCO group.Then it cools down
It is spare with bottom discharge to 60 DEG C.
The preparation of modified epoxy polymer:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 70 parts of bisphenol A type epoxy resin, 5 parts of isooctyl acid and the bis-phenol that epoxide equivalent is 188
F30 parts, it is heated to 130 DEG C after being uniformly mixed, 0.6 part of N is then added, N- dimethyl benzylamine keeps the temperature 6 hours at 140 DEG C,
Obtain a kind of polyepoxides that epoxide equivalent is 1500.Add 4 parts of N- methylethanolamines, 4 parts of amino ethyl ethanolamines
Ketimide, after 120 DEG C are reacted 2 hours.Above-mentioned reaction mixture is cooled to 90 DEG C or less additions, 10 parts of isocyanate curing agents
And 40 parts of above-mentioned cation-modified epoxy resin, 30 minutes are kept the temperature at 70 DEG C, and be cooled to 60 DEG C with bottom discharge, is modified
Epoxide resin polymer is spare.
The preparation of cation-modified polybutadiene epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 50 parts of the dilute resin of the epoxy-modified polybutadiene of Ricon657, MIBK (methyl-isobutyl
Ketone) 20 parts, N, 0.3 part of N- dimethyl benzylamine, 10 parts of N- methyl second of addition are added after 80 DEG C are heated to after being uniformly mixed
The ketimide of hydramine, 10 parts of amino ethyl ethanolamines, the temperature is kept at 120 DEG C 8 hours.In subsequent detection, detection
Amine value cools to 60 DEG C after claimed range.Stirring is warming up to 90 DEG C of heat preservations 4 hours after adding 5 parts of acetic acid and 30 parts of pure water,
And 60 DEG C are cooled to bottom discharge, it is spare to obtain the cation-modified polybutadiene epoxy resin that average molecular weight is 1000.
The preparation of lotion:
Be added in emulsion reactor 25 parts of pure water and 6 parts of acetic acid be stirring evenly and then adding into 50 parts it is above-mentioned cation-modified
After polybutadiene epoxy resin, the 450 parts of above-mentioned modified epoxy polymer of addition in high speed dispersion 5 minutes, then high speed dispersion 1 are small
When after be slowly added 150 parts of deionized waters thereto in two steps every 30 minutes, be further slowly added 100 to it after having added
The deionized water of part, obtains lotion.
The preparation of coating:
Mill base, pure water and lotion are taken according to weight ratio 1:6:5, (conductivity controls 2 μ s/cm of <, temperature control 35 by pure water
DEG C or less) lotion is added after investment groove body, major circulatory system and constant temperature system are opened, adds mill base, final ripening 24 hours
After can carry out coating.
The mill base that the present invention uses, preferably following raw material are made: 40-50 parts of dispersion mill bases are resin dedicated, 38-45 parts of toners
With filler mixture, 1-2 parts of high-boiling point alcohol ethers coalescing agents, 10-15 parts of water.Pigment high speed point is added after above-mentioned raw materials mixing
It dissipates, grind, mill base is obtained by filtration.
Embodiment 2
The preparation of cation-modified epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 500 parts and 500 parts of bisphenol S of Bisphenol F, 135 DEG C are heated to after being uniformly mixed,
Then 0.3 part of triethylamine is added, keeps the temperature 4 hours at 145 DEG C, obtains a kind of polyepoxides that epoxide equivalent is 1000.Add
Add 60 parts of diethylamine, 50 parts of ATBN, is cooled to 60 DEG C after reacting 5 hours at 120 DEG C with bottom discharge, obtaining average molecular weight is
8000 cation-modified epoxy resin is spare.
The preparation of isocyanate curing agent:
It 40 parts of toluene di-isocyanate(TDI), 20 parts, N of methyl iso-butyl ketone (MIBK) (MIBK), 0.5 part of N dimethyl benzylamine, is stirred
It is heated to 70 DEG C after uniformly, is added dropwise 20 parts of sealer imidazoles, so that product temperatur heat preservation promotes temperature extremely after dripping at 60 DEG C
It 70 DEG C, keeps the temperature 1 hour, in subsequent detection, no longer detects NCO group.Then 60 DEG C or less are cooled to go out
Expect spare.
The preparation of modified epoxy polymer:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
Jia Ru not contain the following parts by weight: 60 parts of bisphenol S, 10 parts of formic acid and 80 parts of aromatic type monofunctional epoxy resin stir
It mixes and is heated to 135 DEG C after mixing, 0.3 part of triethanolamine is then added, keep the temperature 4 hours at 145 DEG C, obtain a kind of epoxy and work as
The polyepoxides that amount is 1000.12 parts of dibutyl amine are added, after 130 DEG C are reacted 1 hour.Above-mentioned reaction mixture is cooled to
90 DEG C or less 20 parts of above-mentioned isocyanate curing agents of addition and 20 parts of above-mentioned cation-modified epoxy resin keep the temperature 30 at 80 DEG C
Minute, and 60 DEG C are cooled to bottom discharge, it is spare to obtain modified epoxy polymer.
The preparation of cation-modified polybutadiene epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 70 parts of the dilute resin of the epoxy-modified polybutadiene of JP-200, MIBK (methyl iso-butyl ketone (MIBK))
10 parts, 1 part of -3 imidazoles of 2- methyl add 60 parts of ethylene glycol amines of addition, 180 after being heated to 100 DEG C after being uniformly mixed
DEG C keep the temperature 2 hours.In subsequent detection, amine value is detected after claimed range, cools to 55 DEG C.Add 20 parts of fourths
Stirring is warming up to 100 DEG C and keeps the temperature 2 hours after acid and 10 parts of pure water, and is cooled to 60 DEG C with bottom discharge, obtains average molecular weight
It is spare for 5000 cation-modified polybutadiene epoxy resin.
The preparation of lotion:
35 parts of pure water are added in emulsion reactor and 4 parts of hydrochloric acid are stirring evenly and then adding into 150 parts of above-mentioned cations and change
After property polybutadiene epoxy resin, the 300 parts of above-mentioned modified epoxy polymer of addition in high speed dispersion 5 minutes, then high speed dispersion 1
250 parts of deionized waters were slowly added thereto in two steps every 30 minutes after hour, were further slowly added to it after having added
150 parts of deionized water, obtains lotion.
The preparation of coating:
Mill base, pure water and lotion are taken according to weight ratio 1:4:7, (conductivity controls 2 μ s/cm of <, temperature control 35 by pure water
DEG C or less) lotion is added after investment groove body, major circulatory system and constant temperature system are opened, adds mill base, final ripening 48 hours
After can carry out coating.
Embodiment 3
The preparation of cation-modified epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
Jia Ru not contain the following parts by weight: 900 parts of epoxy resin of aliphatic type difunctional are heated to 132 DEG C, are then added
0.2 part of triethanolamine and 0.3 part of triphenylphosphine keep the temperature 5 hours at 143 DEG C, obtain the poly- epoxy compound that epoxide equivalent is 800
Object.20 parts of dibutyl amine and 30 parts of diethanol amine, 100 parts of ATBN are added, 60 DEG C or less is cooled to after reacting 3 hours at 125 DEG C and goes out
It is spare to obtain the cation-modified epoxy resin that average molecular weight is 5000 for material.
The preparation of isocyanate curing agent:
35 parts of hexamethylene diisocyanate, 25 parts of methyl iso-butyl ketone (MIBK) (MIBK), is stirred by 0.3 part of triethylamine
It is heated to 90 DEG C after even, is added dropwise 20 parts and 5 parts of triethylamine of sealer alkyl alcohol ether, so that product temperatur heat preservation is added dropwise at 65 DEG C
Temperature is promoted after complete to 75 DEG C, is kept the temperature 1.5 hours, in subsequent detection, is no longer detected NCO group.Then
Be cooled to 60 DEG C it is spare with bottom discharge.
The preparation of modified epoxy polymer:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 60 parts of cresol novolaks, 4 parts of benzoic acid, 4 parts of isethionic acid and phenol
60 parts of linear phenol-aldehyde resin, it is heated to 133 DEG C after being uniformly mixed, 0.2 part of triethylamine, 0.3 part of tetramethyl chlorine is then added
Change ammonium, keep the temperature 5 hours at 141 DEG C, obtains a kind of polyepoxides that epoxide equivalent is 1200.Add 5 parts of diethylamine, 5 parts
Ethylene glycol amine, after 125 DEG C are reacted 1.5 hours.It is solid that above-mentioned reaction mixture is cooled to 90 DEG C or less additions, 15 parts of isocyanates
Agent and 30 parts of above-mentioned cation-modified epoxy resin keep the temperature 30 minutes at 75 DEG C, and are cooled to 60 DEG C with bottom discharge, obtain
Modified epoxy polymer is spare.
The preparation of cation-modified polybutadiene epoxy resin:
In a nitrogen environment by the reactor with blender, reflux condensing tube, internal thermometer and nitrogen inlet points
It Jia Ru not contain the following parts by weight: 60 parts of the dilute resin of the epoxy-modified polybutadiene of PB4700, MIBK (methyl iso-butyl ketone (MIBK))
15 parts, 0.3 part of triethylamine and 0.3 part of N, N- dimethylethanolamine, add addition after 90 DEG C are heated to after being uniformly mixed
40 parts of dibutyl amine, the temperature are kept at 150 DEG C 5 hours.In subsequent detection, amine value is detected after claimed range, cooling
To 60 DEG C.Stirring is warming up to 95 DEG C of heat preservations 3 hours after adding 5 parts of formic acid, 5 parts of propionic acid and 20 parts of pure water, and is cooled to 60 DEG C
With bottom discharge, it is spare to obtain the cation-modified polybutadiene epoxy resin that average molecular weight is 2000.
The preparation of lotion:
30 parts of pure water and 3 parts of formic acid are added in emulsion reactor and 2 parts of methacrylic acids are stirring evenly and then adding into 100
After the above-mentioned cation-modified polybutadiene epoxy resin of part, 400 parts of above-mentioned modified epoxies polymerizations are added within high speed dispersion 5 minutes
It was slowly added 150 parts of deionized waters after object, then high speed dispersion 1 hour thereto in two steps every 30 minutes, has added laggard one
It walks and is slowly added 150 parts of deionized water to it, obtain lotion.
The preparation of coating:
Mill base, pure water and lotion are taken according to weight ratio 1:7:4, (conductivity controls 2 μ s/cm of <, temperature control 35 by pure water
DEG C or less) lotion is added after investment groove body, major circulatory system and constant temperature system are opened, mill base is added, it is living that surface is then added
Property agent, can carry out coating after final ripening 36 hours.
The amount of solid content for the isocyanate curing agent that the present invention uses is preferably 70-80%.
The lotion that the present invention obtains has characteristics that solid content: 30-40%, partial size≤80nm, pH value: 5-7, electricity
Conductance (μ s/cm): 1000-2500.
The coating that the present invention is prepared has following characteristic: pH:5.5-6.5, conductivity (μ s/cm): 1000-2000,
MEQA value: (MEQA refers in cathode electro-coating 25-40, carries out titrating required acid to the coating of the part of solid containing 100g
MM number, unit mmol), coulombic efficiency > 30, electrophoretic voltage 80-300V, electrophoresis temperature are 26-30 DEG C, electrophoresis time
For 3min (30 seconds soft starts)；Baking temperature is at 150-160 DEG C, baking time 20-30 minutes；Paint film appearance uniform ground is made
It is smooth, it is adjustable in 10-40 μm of film thickness.
Carry out performance evaluation to using coating provided by the invention to carry out the film that coating obtains: electrophoretic painting is according to following
Standard carries out the test that re-packs: 28 ± 2 DEG C of bath temperature, according to a conventional method at 200 ± 50V energization electrophoresis to 20 ± 2 μm of film thickness.Electrophoresis
After clean, then toast 20min at 160 DEG C, then carry out film performance test.
Comparative example 1
Commercially available conventional coating is chosen, is tested for the property by the same way.
Test result is as follows shown in table 1:
1 test result of table
As seen from the above table, compared with existing product, the cathode electrophoresis dope tool provided by the present application containing butadiene structure
There are good water resistance, low VOC content, good levelling appearance, high throwing power, high sharp edge anti-corrosive properties, the good knot to substrate
With joint efforts, the excellent characteristics such as shock resistance is good.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of cation-modified epoxy resin, which is characterized in that its raw material is based on parts by weight, comprising:
800-1000 parts of epoxy resin compound, 0.3-0.6 parts of basic catalyst, 40-60 parts of aminated compounds and end amino-type
50-200 parts of acrylonitrile-butadiene copolymer.
2. cation-modified epoxy resin according to claim 1, which is characterized in that the epoxy resin compound is selected from
Bisphenol-A, Bisphenol F, bisphenol S, phenol novolaks, cresol novolaks, aliphatic type monofunctional epoxy resin, virtue
One of fragrant race's type monofunctional epoxy resin and aliphatic type bifunctional epoxy resin are a variety of；
Preferably, the basic catalyst is selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl ammonium chloride, triphen
One of base phosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine are a variety of；
It is further preferred that the aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N- methyl ethanol
One of amine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
It is further preferred that the average molecular weight of the cation-modified epoxy resin is 3000-8000.
3. a kind of preparation method of the described in any item cation-modified epoxy resin of claims 1 or 2, which is characterized in that packet
Include following steps:
The epoxy resin compound reacts under the basic catalyst existence condition obtains polyepoxides, the polycyclic
Oxygen compound reacts to obtain the cation-modified asphalt mixtures modified by epoxy resin with the end amino-type acrylonitrile-butadiene copolymer, the aminated compounds
Rouge.
4. a kind of modified epoxy polymer, which is characterized in that its raw material is based on parts by weight, comprising:
Claims 1 or 2 is cation-modified epoxy resin 20-40 parts described in any item, 10-20 parts of isocyanate curing agent,
Second 100-140 parts of epoxy resin compound, 0.3-0.6 parts of the second basic catalyst, 5-10 parts of acid and the second aminated compounds
8-12 parts；
Preferably, it is described acid selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, hydrochloric acid, sulfuric acid, nitric acid,
Sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulfosalicylic acid acid anhydride, first
One of alkyl sulfonic acid and isethionic acid are a variety of；
Preferably, second epoxy resin compound is selected from bisphenol-A, Bisphenol F, bisphenol S, phenol novolaks, cresols
Linear phenol-aldehyde resin, aliphatic type monofunctional epoxy resin, aromatic type monofunctional epoxy resin and aliphatic type difunctionality ring
Oxygen resin it is one or more；
It is further preferred that second basic catalyst is selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl chlorine
Change one of ammonium, triphenylphosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine or a variety of；
It is further preferred that second aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N- methyl
One of ethanol amine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
Preferably, the isocyanate curing agent by the polyisocyanate compound containing one or more isocyanate group with
The sealer that can be added in the isocyanate group reacts to obtain；
It is further preferred that the sealer be selected from alcohol ethers, phenol, lactams, activity methene compound, thio-alcohol,
In sour amides, amine, imidazoles, ureas, carbamates, imines, oximes, sulfites and hydroximic acid esters
It is one or more.
5. a kind of preparation method of modified epoxy polymer as claimed in claim 4, which is characterized in that including following step
It is rapid:
Second epoxy resin compound reaction under the sour existence condition obtains the second polyepoxides；
Then second basic catalyst and second aminated compounds is added, and the reaction was continued；
The isocyanate curing agent and the cation-modified epoxy resin are added after cooling, can go out by keeping the temperature, cooling down
Material.
6. a kind of lotion, which is characterized in that its raw material based on parts by weight, including 25-35 parts of the first pure water, the second 4-6 parts of acid,
Cation-modified polybutadiene epoxy resin 50-150 parts, 300-450 parts of modified epoxy polymer as claimed in claim 4
With 250-400 parts of deionized water；
Preferably, second acid is selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, hydrochloric acid, sulfuric acid, nitre
Acid, sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulfosalicylic acid
One of acid anhydride, Loprazolam and isethionic acid are a variety of.
7. lotion according to claim 6, which is characterized in that the raw material of the cation-modified polybutadiene epoxy resin
Based on parts by weight, comprising: epoxy-modified polybutadiene 50-70 parts, 0.3-1 parts of third basic catalyst, third amine
10-30 parts of 20-60 parts of compound, 5-20 parts of third acid and the second pure water；
Preferably, the third basic catalyst be selected from triethylamine, N, N- dimethyl benzylamine, triethanolamine, tetramethyl ammonium chloride,
One of triphenylphosphine, triethylamine hydrochlorate, -3 imidazoles of 2- methyl and N, N- dimethylethanolamine are a variety of；
It is further preferred that the third aminated compounds is selected from diethylamine, dibutyl amine, ethylene glycol amine, diethanol amine, N- methyl second
One of hydramine, the ketimide of amino ethyl ethanolamine and diethylenetriamine methyl-isobutyl ketimide are a variety of；
It is further preferred that the third acid be selected from formic acid, acetic acid, lactic acid, propionic acid, butyric acid, octanoic acid, valeric acid, caproic acid, hydrochloric acid,
Sulfuric acid, nitric acid, sulfamic acid, acetyl-glycine, benzoic acid, dihydromethyl propionic acid, acrylic acid, methacrylic acid, 2- sulfo group
One of benzoyl oxide, Loprazolam and isethionic acid are a variety of；
It is further preferred that the average molecular weight of the cation-modified polybutadiene epoxy resin is 1000-5000.
8. a kind of preparation method of lotion as claimed in claim 7, which comprises the following steps:
Epoxy-modified polybutadiene is anti-with the third aminated compounds under the third basic catalyst existence condition
It answers；Then the third acid is added and second pure water reacts to obtain the cation-modified polybutadiene epoxy resin；
First pure water, second acid and the cation-modified polybutadiene epoxy resin are mixed to be added after dispersing and changed
The deionized water is added after high speed dispersion in property epoxide resin polymer step by step.
9. a kind of coating, which is characterized in that including mill base, water and the described in any item lotions of claim 6 or 7, the mill base,
The weight ratio of the water and the lotion is 1:4-7:4-7；
Preferably, the coating further includes additive, and the additive includes water-miscible organic solvent, solidification drier, surface
One of activating agent, antioxidant, UV absorbers are a variety of.
10. a kind of application of coating as claimed in claim 9, which is characterized in that be used for cathode electro-coating.
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| CN113563561A (en) * | 2021-08-10 | 2021-10-29 | 广东科力德新材料有限公司 | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste |
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